U.S. patent number 8,603,356 [Application Number 13/260,213] was granted by the patent office on 2013-12-10 for wholly aromatic liquid crystalline polyester resin compound with enhanced fluidity and method of preparing the same.
This patent grant is currently assigned to Samsung Fine Chemicals Co., Ltd.. The grantee listed for this patent is Mahn Jong Kim, Jin Kyu Lee, Youn Eung Lee, Young Hak Shin, Sang Hyuk Suh. Invention is credited to Mahn Jong Kim, Jin Kyu Lee, Youn Eung Lee, Young Hak Shin, Sang Hyuk Suh.
United States Patent |
8,603,356 |
Suh , et al. |
December 10, 2013 |
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( Certificate of Correction ) ** |
Wholly aromatic liquid crystalline polyester resin compound with
enhanced fluidity and method of preparing the same
Abstract
Provided are a wholly aromatic liquid crystalline polyester
resin compound and a method of preparing the same. The wholly
aromatic liquid crystalline polyester resin compound comprises a
first wholly aromatic liquid crystalline polyester resin with a low
melting point, a second wholly aromatic liquid crystalline
polyester resin with a high melting point, and an additive, wherein
the amount of the first wholly aromatic liquid crystalline
polyester resin is 5 to 10 parts by weight with respect to 100
parts by weight of the second wholly aromatic liquid crystalline
polyester resin.
Inventors: |
Suh; Sang Hyuk (Daejeon,
KR), Lee; Youn Eung (Daejeon, KR), Shin;
Young Hak (Daejeon, KR), Lee; Jin Kyu (Busan,
KR), Kim; Mahn Jong (Daejeon, KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Suh; Sang Hyuk
Lee; Youn Eung
Shin; Young Hak
Lee; Jin Kyu
Kim; Mahn Jong |
Daejeon
Daejeon
Daejeon
Busan
Daejeon |
N/A
N/A
N/A
N/A
N/A |
KR
KR
KR
KR
KR |
|
|
Assignee: |
Samsung Fine Chemicals Co.,
Ltd. (Ulsan, KR)
|
Family
ID: |
42936688 |
Appl.
No.: |
13/260,213 |
Filed: |
April 2, 2010 |
PCT
Filed: |
April 02, 2010 |
PCT No.: |
PCT/KR2010/002034 |
371(c)(1),(2),(4) Date: |
September 23, 2011 |
PCT
Pub. No.: |
WO2010/117164 |
PCT
Pub. Date: |
October 14, 2010 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20120022202 A1 |
Jan 26, 2012 |
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Foreign Application Priority Data
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Apr 6, 2009 [KR] |
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10-2009-0029486 |
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Current U.S.
Class: |
252/299.01;
252/299.5; 252/299.67 |
Current CPC
Class: |
C08L
67/03 (20130101); C08L 67/03 (20130101); C08L
2666/18 (20130101); C08L 67/03 (20130101); C08L
2666/18 (20130101); C08K 3/013 (20180101) |
Current International
Class: |
C09K
19/52 (20060101); C08L 67/03 (20060101); C09K
19/54 (20060101); C09K 19/20 (20060101) |
Field of
Search: |
;252/299.01,299.5
;524/425,445,449,451 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1662602 |
|
Aug 2005 |
|
CN |
|
101321803 |
|
Dec 2008 |
|
CN |
|
0396955 |
|
Nov 1990 |
|
EP |
|
0594845 |
|
May 1994 |
|
EP |
|
2158832 |
|
Nov 1985 |
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GB |
|
2002-249647 |
|
Sep 2002 |
|
JP |
|
2003-313403 |
|
Jun 2003 |
|
JP |
|
10-1996-0011007 |
|
Aug 1996 |
|
KR |
|
10-0722949 |
|
May 2007 |
|
KR |
|
10-0773646 |
|
Nov 2007 |
|
KR |
|
04/000937 |
|
Dec 2003 |
|
WO |
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WO 2007052955 |
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May 2007 |
|
WO |
|
Other References
International Search Report, PCT/KR2010/002034, dated Nov. 19,
2010. cited by applicant .
Written Opinion of he International Searching Authority,
PCT/KR2010/002034, dated Nov. 19, 2010. cited by applicant .
Chinese Office Action in Chinese Application No. 201080015782.6,
mailed on Mar. 13, 2013. cited by applicant .
Extended Search Report for European Patent Application No.
10761825.8, mailed on Sep. 9, 2013. cited by applicant .
Office Action for Japanese Patent Application No. 2012-503338,
mailed on Aug. 27, 2013. cited by applicant .
with English Office Action in Japanese Patent Application No.
2012-503338, dated Aug. 27, 2013, with English Translation. cited
by applicant.
|
Primary Examiner: Wu; Shean C
Attorney, Agent or Firm: Nixon Peabody LLP
Claims
The invention claimed is:
1. A wholly aromatic liquid crystalline polyester resin compound
comprising, a first wholly aromatic liquid crystalline polyester
resin with a low melting point, a second wholly aromatic liquid
crystalline polyester resin with a high melting point, and an
additive, wherein the amount of the first wholly aromatic liquid
crystalline polyester resin is 5 to less than 10 parts by weight
with respect to 100 parts by weight of the second wholly aromatic
liquid crystalline polyester resin, wherein melting points of the
first and second wholly aromatic liquid crystalline polyester
resins are 310 to 320.degree. C. and 360 to 375.degree. C.
2. The wholly aromatic liquid crystalline polyester resin compound
of claim 1, wherein the additive includes at least one of an
inorganic filler and an organic filler.
3. The wholly aromatic liquid crystalline polyester resin compound
of claim 2, wherein the inorganic filler includes glass fiber,
talc, calcium carbonate, mica, clay, or a mixture of two or more of
them and the organic filler includes carbon fiber.
Description
CROSS REFERENCE TO RELATED APPLICATIONS or PRIORITY CLAIM
This application is a national phase of International Application
No. PCT/KR2010/002034, which was filed on Apr. 2, 2010, and which
claims priority of Korean Patent Application No. 10-2009-0029486,
filed on Apr. 6, 2009, in the Korean Intellectual Property Office,
the disclosure of which is incorporated herein in its entirety by
reference.
TECHNICAL FIELD
One or more aspects of the present invention relate to wholly
aromatic liquid crystalline polyester resin compounds and methods
of preparing the same, and more particularly, to a wholly aromatic
liquid crystalline polyester resin compound including two or more
kinds of wholly aromatic liquid crystalline polyester resins with
different melting points, and an additive, and a method of
preparing the same.
BACKGROUND ART
Wholly aromatic liquid crystalline polyester resins have good
physical properties of heat resistance, dimensional stability, and
fluidity when being melted, and thus are widely used around the
world, mainly in the electronic parts industry, as materials for
fine injection molding. Particularly, due to excellent dimensional
stability and electricity insulation performance, their usage has
been expanding into films for electronic materials and materials
for substrates.
A wholly aromatic liquid crystalline polyester resin compound used
as materials of fine injection molding requires good fluidity for
producing a compact and lightweight product. To obtain the wholly
aromatic liquid crystalline polyester resin compound with such good
fluidity, a wholly aromatic liquid crystalline polyester resin with
a low melting point has to be used to manufacture the wholly
aromatic liquid crystalline polyester resin compound. However,
usage of the wholly aromatic liquid crystalline polyester resin
with a low melting point in preparing the wholly aromatic liquid
crystalline polyester resin compound causes a problem of degrading
the heat resistance of the wholly aromatic liquid crystalline
polyester resin compound.
DISCLOSURE OF THE INVENTION
Technical Problem
When a wholly aromatic liquid crystalline polyester resin with a
low melting point is used to manufacture the wholly aromatic liquid
crystalline polyester resin compound, usage of the wholly aromatic
liquid crystalline polyester resin with a low melting point in
preparing the wholly aromatic liquid crystalline polyester resin
compound causes a problem of degrading the heat resistance of the
wholly aromatic liquid crystalline polyester resin compound.
Technical Solution
An embodiment of the present invention provides a wholly aromatic
liquid crystalline polyester resin compound including two or more
kinds of wholly aromatic liquid crystalline polyester resins with
different melting points, and an additive.
Another embodiment of the present invention provides a method of
preparing the wholly aromatic liquid crystalline polyester resin
compound.
According to an aspect of the present invention, a wholly aromatic
liquid crystalline polyester resin compound includes a first wholly
aromatic liquid crystalline polyester resin with a low melting
point, a second wholly aromatic liquid crystalline polyester resin
with a high melting point, and an additive, wherein the amount of
the first wholly aromatic liquid crystalline polyester resin is 5
to 10 parts by weight with respect to 100 parts by weight of the
second wholly aromatic liquid crystalline polyester resin.
Melting points of the first and second wholly aromatic liquid
crystalline polyester resins may be 310 to 320.degree. C. and 360
to 375.degree. C.
The additive may include at least one of an inorganic filler and an
organic filler.
The inorganic filler may include glass fiber, talc, calcium
carbonate, mica, clay, or a mixture of two or more of them and the
organic filler includes carbon fiber.
According to another aspect of the present invention, a method of
preparing a wholly aromatic liquid crystalline polyester resin
compound includes mixing a first wholly aromatic liquid crystalline
polyester resin with a low melting point, a second wholly aromatic
liquid crystalline polyester resin with a high melting point, and
an additive, and melt-kneading them, wherein the amount of the
first wholly aromatic liquid crystalline polyester resin is 5 to 10
parts by weight with respect to 100 parts by weight of the second
wholly aromatic liquid crystalline polyester resin.
Advantageous Effects
A wholly aromatic liquid crystalline polyester resin compound with
enhanced fluidity and a method of preparing the same can be
obtained by using two or more kinds of wholly aromatic liquid
crystalline polyester resins with different melting points,
according to an embodiment of the present invention.
MODE FOR INVENTION
A wholly aromatic liquid crystalline polyester resin compound and a
method of preparing the same will now be described in detail
according to an embodiment of the present invention.
According to an embodiment of the present invention, a wholly
aromatic liquid crystalline polyester resin compound includes a
first wholly aromatic liquid crystalline polyester resin with a low
melting point, a second wholly aromatic liquid crystalline
polyester resin with a high melting point, and an additive, wherein
the amount of the first wholly aromatic liquid crystalline
polyester resin is 5 to 10 parts by weight with respect to 100
parts by weight of the second wholly aromatic liquid crystalline
polyester resin. If the amount of the first wholly aromatic liquid
crystalline polyester resin is 5 parts by weight or more with
respect to 100 parts by weight of the second wholly aromatic liquid
crystalline polyester resin, improvement in fluidity in a final
product of the wholly aromatic liquid crystalline polyester resin
compound may be remarkably high, and if the amount of the first
wholly aromatic liquid crystalline polyester resin is 10 parts by
weight or less with respect to 100 parts by weight of the second
wholly aromatic liquid crystalline polyester resin, the possibility
of degrading the heat resistance in the final product of the wholly
aromatic liquid crystalline polyester resin compound may be
reduced.
Melting points of the first and second wholly aromatic liquid
crystalline polyester resins may be 310 to 320.degree. C. and 360
to 375.degree. C., respectively. If the melting point of the first
wholly aromatic liquid crystalline polyester resin is 310.degree.
C. or higher, the possibility of degrading the heat resistance in
the final product of the wholly aromatic liquid crystalline
polyester resin compound may be less and blisters may not be caused
in the wholly aromatic liquid crystalline polyester resin compound,
and if the melting point of the first wholly aromatic liquid
crystalline polyester resin is 320.degree. C. or less, the
enhancement in fluidity may be significantly high. In addition, If
the melting point of the second wholly aromatic liquid crystalline
polyester resin is 360.degree. C. or higher, the possibility of
degrading the heat resistance in the final product of the wholly
aromatic liquid crystalline polyester resin compound may be less,
and if the melting point of the second wholly aromatic liquid
crystalline polyester resin is 375.degree. C. or less, the
enhancement in fluidity may be high, thus making injection molding
easier.
The two or more kinds of wholly aromatic liquid crystalline
polyester resins with different melting points for use in preparing
the wholly aromatic liquid crystalline polyester resin compound may
be prepared by undergoing steps as follows:
(a) synthesizing a wholly aromatic liquid crystalline polyester
prepolymer by condensation polymerization of at least two monomers;
and
(b) synthesizing a wholly aromatic liquid crystalline polyester
resin by solid state polycondensation of the prepolymer.
The monomers used in the step (a) include at least one kind of
compound selected from the group consisting of aromatic diol,
aromatic diamine, and aromatic hydroxylamine; and aromatic
dicarboxylic acid. The monomers may further include aromatic
hydroxycarboxylic acid and/or aromatic amino carboxylic acid.
For step (a), solution condensation polymerization or bulk
condensation polymerization may be used. In addition, monomers
(i.e., acylated monomers) that have been pretreated with a chemical
compound, such as, an acylation agent, particularly, an acetylating
agent, and thus, have improved reactivity, may be used to
facilitate the condensation polymerization of step (a). a. For the
solid state polycondensation of step (b), proper heat needs to be
applied to the prepolymer, and some heat applying methods include a
method of using a hot plate, a method of using hot-air, a method of
using high-temperature fluid. By-products produced during the solid
state polycondensation may be removed by purging with inert gas or
by vacuuming.
The wholly aromatic liquid crystalline polyester resins include
various repeating units in a chain thereof. For example, the
repeating units are as follows: (1) Repeating unit derived from an
aromatic diol: --O--Ar--O-- (2) Repeating unit derived from an
aromatic diamine; --HN--Ar--NH-- (3) Repeating unit derived from an
aromatic hydroxyl amine; --HN--Ar--O-- (4) Repeating unit derived
from an aromatic dicarboxylic acid --OC--Ar--CO-- (5) A repeating
unit derived from an aromatic hydroxycarboxylic acid --O--Ar--CO--
(6) A repeating unit derived from an aromatic amino carboxylic acid
--HN--Ar--CO--
In the formulae defined above, Ar may be phenylene, biphenylene,
naphthalene, an aromatic compound in which two phenylene are bonded
to each other via a carbon or non-carbon element, or an aromatic
compound selected from the group consisting of phenylene,
biphenylene, naphthalene, or two phenylene bonded to each other by
carbon or a non-carbon element in which at least one hydrogen atom
is substituted with other elements.
The additive may include inorganic and/or organic fillers. The
inorganic filler may include glass fiber, talc, calcium carbonate,
mica, clay, or a compound of two or more of them, and the organic
filler may include carbon fiber. The inorganic or organic fillers
may play a role in improving the mechanical strength of a product
obtained by injection molding.
The wholly aromatic liquid crystalline polyester resin compound may
be prepared by mixing two kinds of wholly aromatic liquid
crystalline polyester resins with different melting points and an
additive in a predetermined ratio (i.e., adjusting the amount of a
first wholly aromatic liquid crystalline polyester resin into 5 to
10 parts by weight with respect to 100 parts by weight of a second
wholly aromatic liquid crystalline polyester resin) and
melt-kneading them. A batch type mixer, a twin screw extruder, or a
mixing-roll may be used for such melt-kneading. In addition, a
lubricant may be used during the melt-kneading for smooth
melt-keading.
Reference will now be made in detail to embodiments to describe the
invention. In this regard, the present embodiments may have
different forms and should not be construed as being limited to the
descriptions set forth herein.
Example 1
(1) Selection of Wholly Aromatic Liquid Crystalline Polyester
Resins
A KF grade wholly aromatic polyester resin provided by Samsung Fine
Chemicals Co., Ltd. was used as a wholly aromatic liquid
crystalline polyester resin with a low melting point. Using
Differential Scanning calorimetry (DSC), the melting point of the
resin was measured to be 315.degree. C. A KB grade wholly aromatic
polyester resin provided by Samsung Fine Chemicals Co., Ltd. was
used as a wholly aromatic liquid crystalline polyester resin with a
high melting point. Using the DSC, the melting point of the wholly
aromatic liquid crystalline polyester resin was measured to be
363.degree. C.
(2) Preparation of a Wholly Aromatic Liquid Crystalline Polyester
Resin Compound
A wholly aromatic liquid crystalline polyester resin compound was
prepared by mixing the two kinds of wholly aromatic liquid
crystalline polyester resins having different melting points and a
glass fiber (e.g., a ground glass fiber with 10 .mu.m in diameter
and 150 .mu.m in average length) in the weight ratio 6:4 (i.e.,
resins: glass fiber) and melt-kneading them with a twin screw
extruder (with 40 in L/D and 25 mm in diameter). In this case,
inputs of the KF grade wholly aromatic liquid crystalline polyester
resin with a low melting point and the KB grade wholly aromatic
liquid crystalline polyester resin with a high melting point were
adjusted to 3 and 57 parts by weight, respectively, with respect to
100 parts by weight of the final wholly aromatic liquid crystalline
polyester resin compound. During the preparation of the wholly
aromatic liquid crystalline polyester resin compound, by-products
were removed by the twin screw extruder under vacuum.
Example 2
The same method as in Example 1 was applied to prepare the wholly
aromatic liquid crystalline polyester resin compound except that
inputs of the KF grade wholly aromatic liquid crystalline polyester
resin with a low melting point and the KB grade wholly aromatic
liquid crystalline polyester resin with a high melting point were
adjusted to 5 and 55 parts by weight, respectively, with respect to
100 parts by weight of the final wholly aromatic liquid crystalline
polyester resin compound.
Comparative Example 1
The same method as in Example 1 was applied to prepare the wholly
aromatic liquid crystalline polyester resin compound except that an
input of the KB grade wholly aromatic liquid crystalline polyester
resin with a high melting point was adjusted to 60 parts by weight
with respect to 100 parts by weight of the final wholly aromatic
liquid crystalline polyester resin compound, without using the KF
grade wholly aromatic liquid crystalline polyester resin with a low
melting point at all.
Comparative Example 2
The same method as in Example 1 was applied to prepare the wholly
aromatic liquid crystalline polyester resin compound except that
inputs of the KF grade wholly aromatic liquid crystalline polyester
resin with a low melting point and the KB grade wholly aromatic
liquid crystalline polyester resin with a high melting point were
adjusted to 1 and 59 parts by weight, respectively, with respect to
100 parts by weight of the final wholly aromatic liquid crystalline
polyester resin compound.
Comparative Example 3
The same method as in Example 1 was applied to prepare the wholly
aromatic liquid crystalline polyester resin compound except that
inputs of the KF grade wholly aromatic liquid crystalline polyester
resin with a low melting point and the KB grade wholly aromatic
liquid crystalline polyester resin with a high melting point were
adjusted to 7 and 53 parts by weight, respectively, with respect to
100 parts by weight of the final wholly aromatic liquid crystalline
polyester resin compound.
Evaluation Example 1
Fluidity Measurement
In order to measure fluidity of the wholly aromatic liquid
crystalline polyester resin compounds resulting from Examples 1 and
2 and Comparative Examples 1 to 3, a capillary viscometer was used
to measure a respective melt viscosity of the wholly aromatic
liquid crystalline polyester resin compounds at a temperature of
380.degree. C. and a shear rate of 1000/s. The melt viscosities of
the wholly aromatic liquid crystalline polyester resin compounds
are shown in Table 1 below. Low melt viscosity means high
fluidity.
(Heat Resistance Measurement)
Injection molded test specimens were manufactured from the wholly
aromatic liquid crystalline polyester resin compounds resulting
from Examples 1 and 2 and Comparative Examples 1 to 3, and heat
resistance of the respective test specimens was evaluated. A form
of the test specimens and a measurement scheme of heat resistance
was set based on ASTM D648 and the applied pressure was 18.5
kgf/cm.sup.2.
TABLE-US-00001 TABLE 1 Com- Com- Com- Ex- parative parative
parative Classification Example 1 ample 2 Example 1 Example 2
Example 3 Fluidity 464 257 1425 1217 173 (poise) Heat 319 318 319
319 309 Resistance (.degree. C.)
Referring to Table 1, both fluidity and heat resistance of the
wholly aromatic liquid crystalline polyester resin compounds
resulting from Examples 1 and 2 were found to be good. On the other
hand, either fluidity or heat resistance of the wholly aromatic
liquid crystalline polyester resin compounds resulting from
Comparative Examples 1 to 3, was found to be too low. In
conclusion, the wholly aromatic liquid crystalline polyester resin
compounds according to an embodiment of the present invention may
be valuably used as materials for fine injection molding.
It should be understood that the exemplary embodiments described
therein should be considered in a descriptive sense only and not
for purposes of limitation. Descriptions of features or aspects
within each embodiment should typically be considered as available
for other similar features or aspects in other embodiments.
* * * * *